CN100390205C - Solid titanium catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for olefin polymerization - Google Patents
Solid titanium catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for olefin polymerization Download PDFInfo
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- CN100390205C CN100390205C CNB038067641A CN03806764A CN100390205C CN 100390205 C CN100390205 C CN 100390205C CN B038067641 A CNB038067641 A CN B038067641A CN 03806764 A CN03806764 A CN 03806764A CN 100390205 C CN100390205 C CN 100390205C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/06—Catalyst characterized by its size
Abstract
Disclosed is a catalyst for olefin polymerization comprising [I] a solid titanium catalyst component [S] comprising titanium, magnesium, halogen and an electron donor (b), which is obtained by bringing a solid adduct consisting of a magnesium compound and an electron donor (a) into contact with an electron donor (b) and a liquid titanium compound by at least one method selected from (A) a method of contacting the materials in a suspended state in the coexistence of an inert hydrocarbon solvent and (B) a method of contacting the materials plural times in divided portions and [II] an organometallic compound catalyst component [M] containing a metal selected from the groups I to II in the periodic table. By olefin polymerization with this polymerization catalyst, an olefinic (co)polymer having high stereospecificity can be obtained with high activity.
Description
Technical field
The present invention relates to a kind of solid catalyst composition, a kind of catalyzer and a kind of method that is used to prepare the homopolymer or the multipolymer of ethene and alpha-olefin.
Background technology
A kind ofly contain a kind of catalyzer that loads on titanium compound on the magnesium halide, in its active state, the catalyzer in using as preparation olefin polymer such as ethene or alpha-olefin homo or ethylene/alpha-olefin copolymer is well-known.
As for olefin polymerization catalyst (hereinafter " olefin polymerization catalyst " is used for comprising " copolyreaction catalyzer " sometimes), a kind of solid titanium catalyst composition and a kind of organometallic compound that contains magnesium, titanium, halogen and a kind of electron donor(ED) is known.
This catalyzer is in the polyreaction or copolyreaction of alpha-olefin such as propylene and butene-1, similar to ethylene polymerization, has very high activity (hereinafter, " polyreaction " is used for comprising " copolyreaction " sometimes), the stereospecific of resulting polymkeric substance also is very high (hereinafter, " polymkeric substance " is used for comprising " multipolymer " sometimes).
In these catalyzer, a kind ofly use load on it a kind of solid titanium catalyst composition that carboxylicesters typically is the electron donor(ED) of phthalic ester, a kind of al-alkyl compound of being selected to be arranged as a kind of catalyst component and a kind of catalyzer with silicon compound of at least one Si-OR key (R is alkyl), known have a good performance.
The inventor is in order to obtain a kind of the have better polymerization activity and the olefin polymerization catalyst of stereospecific, carried out deep research, consequently, they find, this purpose can have magnesium by a kind of use is a kind of, halogen, the specific solid state titanium catalyst component of titanium and a kind of electron donor(ED) (b), with a kind of catalyzer of organometallic compound and realize, perhaps, can contain a kind of magnesium that has by a kind of, titanium, specific solid state titanium catalyst component with a kind of electron donor(ED) (b), a kind of organometallic compound, with the catalyzer of a kind of electron donor(ED) (c) and realize.
Summary of the invention
The present invention finishes under these situations, the objective of the invention is to be used to provide a kind of solid titanium catalyst composition that is used for olefinic polyreaction, it is by using the specific electron that is obtained by a kind of specific preparation method to obtain for body, and a kind of alkene (being total to) polymkeric substance with high stereospecific and high catalytic activity, make by alkene (being total to) polyreaction by using described solid-state titanium composition.
The present invention is used for the solid titanium catalyst composition [S] of olefinic polyreaction, it contains titanium, magnesium, halogen and a kind of electron donor(ED) (b), be to adopt at least a method in following two kinds of methods to make: the catalyst component that is suspended in a kind of unreactive hydrocarbons solvent is contacted, the method that catalyst component is contacted in batches repeatedly with (B) by a kind of solid adduct of being made up of a kind of magnesium compound and a kind of electron donor(ED) (a) is contacted with a kind of liquid titanium compound with a kind of electron donor(ED) (b).
The solid titanium catalyst composition that is used for olefinic polyreaction in the present invention, a kind of compound with two or more ehter bonds can be used as described electron donor(ED) (b), be used for obtaining a kind of olefin polymerization catalyst, this catalyzer can very high activity make a kind of polymkeric substance with high stereospecific, and does not need to re-use a kind of electron donor(ED) when the described polymerisation catalysts of preparation.
The particle diameter of solid titanium catalyst composition that is used for olefinic polyreaction as the present invention is in the scope of 30-150 μ m the time, causes the mobility of particle problem of operating barrier when the preparation segmented copolymer to the polymerizer owing to described particle adhesion, just can be reduced.
Olefin polymerization catalyst of the present invention comprises a kind of titanium that contains, magnesium, the solid titanium catalyst composition [S] of halogen and a kind of electron donor(ED) (b), contain a kind of Organometal compound catalyst composition [M] that is selected from the metal of I-III family in the periodic table of elements with a kind of, described solid titanium catalyst composition [S], be to adopt at least a method in following two kinds of methods to make: the catalyst component that is suspended in a kind of unreactive hydrocarbons solvent is contacted, the method that catalyst component is contacted in batches repeatedly with (B) by a kind of solid adduct of being made up of a kind of magnesium compound and a kind of electron donor(ED) (a) is contacted with a kind of liquid titanium compound with a kind of electron donor(ED) (b).
Process for olefin polymerization of the present invention comprises by using at least a ethene and the C of being selected from of above-mentioned olefin polymerization catalyst polymerization or copolymerization
3-20The alkene of alpha-olefin.
In olefin polymerization catalyst of the present invention and process for olefin polymerization, described Organometal compound catalyst composition [M], can use with solid titanium catalyst composition of the present invention [S], so that carry out described polyreaction effectively, obtain having the polymkeric substance of high stereospecific with high catalytic activity.
In olefin polymerization catalyst of the present invention and process for olefin polymerization, except described two kinds of compositions are that described solid titanium catalyst composition [S] and described Organometal compound catalyst composition [M] are thought, can also use and contain the catalyzer that a kind of specific electron is given body (c), to obtain a kind of more polymkeric substance of high stereospecific that has.
Implement best mode of the present invention
Hereinafter, the present invention is used for solid catalyst composition, olefin polymerization catalyst and the process for olefin polymerization of olefinic polyreaction, will obtain more detailed description.
The present invention is used for the solid titanium catalyst composition [S] of olefinic polyreaction, be to adopt at least a method in following two kinds of methods to make: (A) under a kind of unreactive hydrocarbons solvent coexistence by a kind of solid adduct of being made up of a kind of magnesium compound and a kind of electron donor(ED) (a) is contacted with a kind of liquid titanium compound with a kind of electron donor(ED) (b), the method that described material is contacted with suspended state, the method that in batches described material is contacted with (B).
That is to say that according to the method (P-1)-(P-3) that described electron donor(ED) (b) contacts with a kind of liquid titanium compound, the solid titanium catalyst composition [S] that the present invention is used for olefinic polyreaction can be divided into solid titanium catalyst composition [S1]-[S3].
Described solid titanium catalyst composition [S1] makes by described method (P-1), this method is to be undertaken by a kind of solid adduct of being made up of a kind of magnesium compound and a kind of electron donor(ED) (a) is contacted with a kind of liquid titanium compound with a kind of electron donor(ED) (b), it adopts under a kind of unreactive hydrocarbons solvent coexistence, the method (A) that described material is contacted with suspended state.
Described solid titanium catalyst composition [S2] makes by described method (P-2), this method is to be undertaken by a kind of solid adduct of being made up of a kind of magnesium compound and a kind of electron donor(ED) (a) is contacted with a kind of liquid titanium compound with a kind of electron donor(ED) (b), and it adopts the method (B) that described material is contacted.
Described solid titanium catalyst composition [S3] makes by described method (P-3), this method is to be undertaken by a kind of solid adduct of being made up of a kind of magnesium compound and a kind of electron donor(ED) (a) is contacted with a kind of liquid titanium compound with a kind of electron donor(ED) (b), it adopts under the coexistence of a kind of unreactive hydrocarbons solvent, makes described material contact with the method (A) that described material is contacted with suspended state and (B).
Olefin polymerization catalyst of the present invention comprises above-mentioned described solid titanium catalyst composition [S].
Hereinafter, will described magnesium compound and the described electron donor(ED) (a) that be used as described solid-state adducts starting raw material among the present invention be described, then method and the resulting thus solid-state adducts for preparing described solid-state adducts described.
Afterwards, described titanium compound and described electron donor(ED) (b) as described solid titanium catalyst composition [S] starting raw material are described.As for described electron donor(ED) (b), will describe electron donor(ED) (b1) and electron donor(ED) (b2) respectively.
Afterwards, will describe with the described method that described material is contacted to prepare described solid titanium catalyst composition [S2] the embedding hydrocarbon solvent that in described solid titanium catalyst composition [S1] preparation, uses, the preparation method of described solid titanium catalyst composition [S1].
Afterwards, to describe described Organometal compound catalyst composition [M], at last, the application of the invention olefin polymerization catalyst being carried out the described electron donor(ED) (c) that (if desired) used in the method for olefinic polyreaction and the described polyreaction describes.
[magnesium compound]
The middle described solid-state adducts that uses of described solid titanium catalyst composition [S] used in preparation the present invention is formed by a kind of magnesium compound and described electron donor(ED) (a), and described magnesium compound comprises, for example: magnesium halide such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; Alkoxyl group magnesium halide such as methoxyl group chlorination magnesium and oxyethyl group magnesium chloride; Aryloxy magnesium halide such as phenoxy group magnesium chloride; Alkoxyl magnesium such as magnesium ethylate, isopropoxy magnesium, butoxy magnesium and 2-ethyl hexyl oxy magnesium; Aryloxy magnesium such as phenoxy group magnesium; With magnesium carboxylates such as Magnesium monolaurate and Magnesium Stearate.
These magnesium compounds can use separately, and they also can be used in combination.Title complex or dinuclear complex that these magnesium compounds can be used as with a kind of other metal use, and the mixture that also can be used as with a kind of other metallic compound uses.
In these compounds, magnesium halide particularly magnesium chloride is preferred the employing.Described magnesium compound can obtain from another kind of raw material.
[electron donor(ED) (a)]
As for described electron donor(ED) [a], can use a kind of compound with the described magnesium compound ability of dissolving.Described compound preferably alcohol, aldehyde, amine, carboxylic acid or its mixture with the described magnesium compound ability of dissolving.
Described alcohol with the described magnesium compound ability of dissolving, for instance, comprising: fatty alcohol such as methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, two oxalic acid monomethyl ethers, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, decyl alcohol and dodecanol; Alicyclic ring alcohol such as hexalin and methyl-cyclohexanol; Aromatic alcohol such as phenylcarbinol and methylbenzyl alcohol; With fatty alcohol that contains an alkoxyl group such as normal-butyl cellosolve.
Described carboxylic acid comprises C7 or bigger organic carboxyl acid such as sad or 2 ethyl hexanoic acid.Described aldehyde comprises C7 or bigger aldehyde such as capraldehyde and 2-ethyl hexanal.
Described amine comprises C6 or bigger amine such as heptyl amice, octylame, nonyl amine, lauryl amine and 2 ethyl hexylamine.
Described electron donor(ED) (a) is preferably a kind of alcohol, is preferably ethanol, propyl alcohol or butanols especially.
[preparation method of described solid-state adducts]
The described solid-state adducts that uses in the described solid titanium catalyst composition of preparation [S] can prepare by described magnesium compound is contacted with described electron donor(ED) (a).Described solid-state adducts is preferably a kind of to contact the title complex that makes by magnesium chloride with a kind of alcohol.
When the described solid-state adducts of preparation, the quantity of used magnesium compound and electron donor(ED) (a), type and contact conditions according to them change, but normally, the consumption of described magnesium compound, based on the described electron donor(ED) of unit volume (a), its quantity is 0.1-20mol/L, is preferably 0.5-5mol/L.
[titanium compound]
Be used to prepare the described liquid titanium compound of the composition of solid titanium catalyst described in the present invention [S], comprise the tetravalent titanium compound of representing by following general formula:
Ti(OR)
gX
4-g
Wherein, R is an alkyl, and X is a halogen atom, and g satisfies the relational expression of 0≤g≤4.The particular instance of this class titanium compound comprises: titanium tetrahalide such as TiCl
4, TiBr
4And TiI
4Alkoxyl group three halogenated titaniums such as Ti (OCH
3) Cl
3, Ti (OC
2H
5) Cl
3, Ti (O-n-C
4H
9) Cl
3, Ti (OC
2H
5) Br
3And Ti (O-iso-C
4H
9) Br
3Alkoxyl group dihalide titanium such as Ti (OCH
3)
2Cl
2, Ti (OC
2H
5)
2Cl
2, Ti (O-n-C
4H
9)
2Cl
2And Ti (OC
2H
5)
2Br
2Alkoxyl group list halogenated titanium such as Ti (OCH
3)
3Cl, Ti (OC
2H
5)
3Cl, Ti (O-n-C
4H
9)
3Cl and Ti (OC
2H
5)
3Br; With four titan-alkoxides such as Ti (OCH
3)
4, Ti (OC
2H
5)
4, Ti (O-n-C
4H
9)
4, Ti (O-iso-C
4H
9)
4And Ti (O-2-ethylhexyl) 4.
In these materials, preferably titanium tetrahalide is preferably titanium tetrachloride especially.These titanium compounds can use separately, and form that also can its mixture is used.
[electron donor(ED) (b)]
In solid titanium catalyst composition of the present invention [S], except above-claimed cpd, also use described electron donor(ED) (b).Can be used for the described electron donor(ED) (b) among the present invention, comprise: have two or more electron donor(ED)s (b1) and other electron donor(ED) (b2) via the ehter bond of a plurality of atoms, and in the present invention, described electron donor(ED) (b1) preferably uses based on the high polymerization activity purpose.Hereinafter, will describe described electron donor(ED) (b1) and electron donor(ED) (b2).
[electron donor(ED) (b1)]
Described to have two or more electron donor(ED)s via the ehter bond of a plurality of atoms (b1) be a kind of like this compound, and it (that is to say between C-O-C and C-O-C) to have a plurality of atoms between at least two ehter bonds (C-O-C).Especially, described compound (b1) is a kind of like this compound, and wherein, at least two ehter bonds (C-O-C) connect via a plurality of atoms, described atom is carbon atom, Siliciumatom, Sauerstoffatom, sulphur atom, phosphorus atom or boron atom, or is selected from two or more atoms wherein.
The atom that connects these ehter bonds can have one or more substituting groups, and this substituting group contains at least a element that is selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulphur, phosphorus, boron and silicon.Described compound is preferably a kind of like this compound, and wherein, the substituting group that one or two is big relatively is to be connected to one on the atom between the ehter bond, and the described atom that connects ehter bond contains a plurality of carbon atoms.
Described compound with two or more ehter bonds for instance, comprises the compound by following general formula (1) expression:
Wherein, n is an integer that satisfies 2≤n≤10 relational expressions, R
1-R
26In each the expression substituting group, this substituting group has at least a element that is selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulphur, phosphorus, boron and silicon, R
1-R
26In any group, preferred R
1-R
2n, can be combined together to form a kind of ring of non-phenyl ring, and its main chain can contain the atom of non-carbon.
Above-mentioned compound with two or more ehter bonds for instance, comprising:
2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal,
2-sec.-propyl-1, the 3-Propanal dimethyl acetal,
2-butyl-1, the 3-Propanal dimethyl acetal,
2-sec-butyl-1, the 3-Propanal dimethyl acetal,
2-cyclohexyl-1, the 3-Propanal dimethyl acetal,
2-phenyl-1, the 3-Propanal dimethyl acetal,
2-cumyl-1, the 3-Propanal dimethyl acetal,
2-sec.-propyl-2-isobutyl--1, the 3-Propanal dimethyl acetal,
2-(2-phenylethyl)-1, the 3-Propanal dimethyl acetal,
2-(2-cyclohexyl ethyl)-1, the 3-Propanal dimethyl acetal,
2,2-dicyclohexyl-1, the 3-Propanal dimethyl acetal,
2,2-diethyl-1, the 3-Propanal dimethyl acetal,
2,2-dipropyl-1, the 3-Propanal dimethyl acetal,
2,2-dibutyl-1, the 3-Propanal dimethyl acetal,
2-methyl-2-propyl group-1, the 3-Propanal dimethyl acetal,
2-methyl-2-benzyl-1, the 3-Propanal dimethyl acetal,
2-methyl-2-ethyl-1, the 3-Propanal dimethyl acetal,
2-methyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal,
2-methyl-2-phenyl-1, the 3-Propanal dimethyl acetal,
2-methyl-2-cyclohexyl-1, the 3-Propanal dimethyl acetal,
2-methyl-2-isobutyl--1, the 3-Propanal dimethyl acetal,
2,2-diisobutyl-1, the 3-Propanal dimethyl acetal,
2,2-phenylbenzene-1, the 3-Propanal dimethyl acetal,
2,2-two (cyclohexyl methyl)-1, the 3-Propanal dimethyl acetal,
2,2-diisobutyl-1, the 3-di ethyl propyl ether,
2,2-diisobutyl-1,3-dibutoxy propane,
2-isobutyl--2-sec.-propyl-1, the 3-Propanal dimethyl acetal,
2,2-two-sec-butyl-1, the 3-Propanal dimethyl acetal,
2,2-two-tertiary butyl-1, the 3-Propanal dimethyl acetal,
2,2-di neo-pentyl-1, the 3-Propanal dimethyl acetal,
2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal,
2-cyclohexyl-2-cyclohexyl methyl-1, the 3-Propanal dimethyl acetal,
2,3-phenylbenzene-1,4-diethoxy butane,
2,3-dicyclohexyl-1,4-diethoxy butane,
2,3-dicyclohexyl-1,4-diethoxy butane,
2,3-di-isopropyl-1,4-diethoxy butane,
2,4-phenylbenzene-1,5-dimethoxy pentane,
2,5-phenylbenzene-1,5-dimethoxy hexane,
2,4-di-isopropyl-1,5-dimethoxy pentane,
2,4-diisobutyl-1,5-dimethoxy pentane,
2,4-diisoamyl-1,5-dimethoxy pentane,
1,2-two isobutoxy propane,
1,2-two isobutoxy ethane,
1,3-diisoamyl oxygen base ethane,
1,3-diisoamyl oxygen base propane,
1,3-two different neopentyl oxygen ethane,
1,3-two neopentyl oxygen propane,
1,2-two (methoxymethyl) hexanaphthene,
3,3-diisobutyl-1,5-oxo nonane,
6,6-dibutyl dioxy heptane,
1,1-dimethoxy-methyl pentamethylene,
2-methyl-2-methoxymethyl-1, the 3-Propanal dimethyl acetal,
2-cyclohexyl-2-ethoxyl methyl-1, the 3-di ethyl propyl ether,
2-cyclohexyl-2-methoxymethyl-1, the 3-Propanal dimethyl acetal,
2,2-diisobutyl-1,3-dimethoxy hexanaphthene,
2-sec.-propyl-2-isopentyl-1,3-dimethoxy hexanaphthene,
2-cyclohexyl-2-methoxymethyl-1,3-dimethoxy hexanaphthene,
2-sec.-propyl-2-methoxymethyl-1,3-dimethoxy hexanaphthene,
2-isobutyl--2-methoxymethyl-1,3-dimethoxy hexanaphthene,
2-cyclohexyl-2-ethoxyl methyl-1,3-dimethoxy hexanaphthene,
2-sec.-propyl-2-ethoxyl methyl-1,3-dimethoxy hexanaphthene,
2-isobutyl--2-ethoxyl methyl-1,3-dimethoxy hexanaphthene,
Phenylbenzene two (methoxymethyl) silane,
Two-tertiary butyl-two (methoxymethyl) silane and
Cyclohexyl-tertiary butyl-two (methoxymethyl) silane.
In these compounds, preferably 1, the 3-diether is preferably 2-sec.-propyl-2-isobutyl--1 especially, 3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal and 2,2-two (cyclohexyl methyl)-1,3-Propanal dimethyl acetal.
[electron donor(ED) (b2)]
Contained described solid titanium catalyst composition [S] in the olefin polymerization catalyst of the present invention can substitute described electron donor(ED) (b1) with two or more ehter bonds by described electron donor(ED) (b2) and prepare.Described electron donor(ED) (b2) for instance, comprises organic ester and organic acid anhydride, described in the EP585869A1 of the applicant's submission.
Used electron donor(ED) (b2) is preferably a kind of carboxylicesters, and more preferably a kind of multivalent carboxylate is preferably a kind of phthalic ester again.
As mentioned above, the described electron donor(ED) (b) that is used for the present invention is preferably described two or more compounds via the ehter bond of a plurality of atoms (b1) that have, and more preferably a kind of compound by above-mentioned general formula (1) expression is preferably 1, the 3-diether especially.This class 1, the particularly preferred form of 3-diether as mentioned above.When the described solid titanium catalyst composition of preparation, a kind of described electron donor(ED) (b1) and mixture (b2) also can be used as described electron donor(ED) (b).
[preparing described solid titanium catalyst composition [S1]]
Solid titanium catalyst composition of the present invention [S1] is by under a kind of unreactive hydrocarbons solvent coexistence, described solid-state adducts is contacted with described liquid titanium compound with described electron donor(ED) (b) make.
Hereinafter, the embodiment of the described solid titanium catalyst compositions of several preparations [S1] (hereinafter being also referred to as " solid-state titanium complex ") is illustrated, but the present invention is not limited to this class methods.
(P-a) described solid-state titanium complex is by under a kind of unreactive hydrocarbons solvent coexistence, and described solid-state adducts is contacted with described electron donor(ED) (b), described liquid titanium compound is contacted with resulting product prepare.
(P-b) described solid-state titanium complex is by under a kind of unreactive hydrocarbons solvent coexistence, and described solid-state adducts is contacted with described liquid titanium compound, described electron donor(ED) (b) is contacted with resulting product prepare.
(P-c) described solid-state titanium complex is by under a kind of unreactive hydrocarbons solvent coexistence, described solid-state adducts is contacted with a kind of halogen contained compound and/or a kind of organometallic compound with described electron donor(ED) (b), described liquid titanium compound is contacted with resulting product prepare.
(P-d) described solid-state titanium complex is by under a kind of unreactive hydrocarbons solvent coexistence, described solid-state adducts is contacted with described liquid titanium compound, described electron donor(ED) (b) and a kind of halogen contained compound and/or a kind of organometallic compound are contacted with resulting product prepare.
Described liquid titanium compound also can further contact with the solid titanium catalyst composition [S1] that obtains in the aforesaid method (P-a) to (P-d).
Described unreactive hydrocarbons solvent for instance, comprising: aliphatic hydrocrbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; Alicyclic hydrocarbon such as pentamethylene, hexanaphthene and methylcyclopentane; Aromatic hydrocarbon such as benzene, toluene and dimethylbenzene; Halohydrocarbon such as vinylchlorid and chlorobenzene; Or its mixture.
In these unreactive hydrocarbons solvents, aliphatic hydrocrbon or aromatic hydrocarbon are preferred the uses, and octane, decane, toluene and dimethylbenzene more preferably use.
When preparing described solid titanium catalyst composition [S1] by these methods, the quantity of used described solid-state adducts, described liquid titanium compound and described electron donor(ED) (b), will change according to their type, contact conditions and engagement sequence, but, preferably, with respect to every mole of magnesium in the solid-state adducts of forming by described magnesium compound and described electron donor(ED) (a), the consumption of described electron donor(ED) (b) is 0.01-5mol, be preferably 0.1-1mol especially, the consumption of described liquid titanium compound is 0.1-1000mol, is preferably 1-200mol especially.The consumption of described unreactive hydrocarbons solvent is preferably 0.0001-100mol, is preferably 0.0001-0.1mol especially.
The temperature that these compounds contact is generally-70 ℃ to 200 ℃, and preferred temperature is-25 ℃ to 150 ℃.
Through this described solid titanium catalyst composition [S1] that makes, contain titanium, magnesium and halogen and described electron donor(ED) (b).
In described solid titanium catalyst composition [S1], the ratio (atomic ratio) of halogen/titanium is 2-100, be preferably 4-90, when using described electron donor(ED) (b1) as described electron donor(ED) (b), the ratio (mol ratio) of electron donor(ED) (b1)/titanium is 0.01-100, be preferably 0.2-10, the ratio (atomic ratio) of magnesium/titanium is 2-100, is preferably 4-50.On the other hand, when using described electron donor(ED) (b2) as described electron donor(ED) (b), the ratio (mol ratio) of electron donor(ED) (b2)/titanium is 0.01-100, is preferably 0.2-10, and the ratio (atomic ratio) of magnesium/titanium is 2-100, is preferably 4-50.，
[preparing described solid titanium catalyst composition [S2]]
Solid titanium catalyst composition of the present invention [S2] contacts with described liquid titanium compound and makes by make described solid-state adducts, described electron donor(ED) (b) each other in batches repeatedly.As for described electron donor(ED) (b), described electron donor(ED) (b1) and (b2) all can use without restriction, but, in order to obtain higher polymerization activity, described electron donor(ED) (b1), just, described compound with two or more ehter bonds via a plurality of atoms is preferably used as described electron donor(ED) (b).
The described method for preparing solid titanium catalyst composition [S2] is not particularly limited, and this method can obtain explanation by means of a plurality of embodiment.In the present invention, " repeatedly " is defined as twice or more times, but at following preparation embodiment (P-a ') in (P-d '), described material is twice of contact.Described have the compound of two or more ehter bonds as described electron donor(ED) (b).
(P-a ') described solid-state adducts contacts with described compound with two or more ehter bonds, described solid-state titanium compound contacts with resulting product, obtain a kind of solid titanium catalyst composition precursor [S2 '], described solid titanium catalyst composition precursor [S2 '] contact once more with described compound with two or more ehter bonds, described liquid titanium compound contacts once more with resulting product, obtains described solid titanium catalyst composition [S2].
(P-b ') described solid-state adducts contacts with described liquid titanium compound, described compound with two or more ehter bonds contacts with resulting product, obtain a kind of solid titanium catalyst composition precursor [S2 '], described solid titanium catalyst composition precursor [S2 '] contact once more with described liquid titanium compound, described compound with two or more ehter bonds contacts once more with resulting product, obtains described solid titanium catalyst composition [S2].
(P-c ') described solid-state adducts contacts with a kind of halogen contained compound and/or a kind of organometallic compound with described compound with two or more ehter bonds, described liquid titanium compound contacts with resulting product, obtain a kind of solid titanium catalyst composition precursor [S2 '], described solid titanium catalyst composition precursor [S2 '] contact once more with a kind of halogen contained compound and/or a kind of organometallic compound with described compound with two or more ehter bonds, described liquid form mixt contacts once more with resulting product, obtains described solid titanium catalyst composition [S2].
(P-d ') described solid-state adducts contacts with described liquid titanium compound, described compound with two or more ehter bonds contacts with resulting product with a kind of halogen contained compound and/or a kind of organometallic compound, obtain a kind of solid titanium catalyst composition precursor [S2 '], described solid titanium catalyst composition precursor [S2 '] contact once more with described liquid titanium compound, described compound with two or more ehter bonds contacts with resulting product once more with a kind of halogen contained compound and/or a kind of organometallic compound, obtains described solid titanium catalyst composition [S2].
Described compound with two or more ehter bonds also can further contact with the described composition that aforesaid method (P-a ') obtains in (P-d ').
When preparing described solid titanium catalyst composition [S2] by these methods, used described solid-state adducts, described liquid titanium compound and described quantity with compound of two or more ehter bonds, will change according to their type, contact conditions, engagement sequence and contact frequency, but, normally, with respect to every mole of magnesium in the solid-state adducts of forming by described magnesium compound and described electron donor(ED) (a), described consumption with compound of two or more ehter bonds is 0.01-5mol, be preferably 0.1-2.0mol, more preferably 0.1-1.5mol.When described material is contact twice time, described consumption with compound of two or more ehter bonds more preferably, be 0.1-1.0mol in first contact, is 0.1-0.5mol in second contacts.The consumption of described liquid titanium compound with respect to every mole of magnesium in the described solid-state adducts, is 0.1-1000mol, is preferably 1-200mol especially.Described liquid titanium compound can disposable whole addings, also can add in batches.Normally, described liquid titanium compound can join wherein in described solid-state adducts or described solid titanium catalyst composition and described compound portion-wise addition with two or more ehter bonds.
Described solid-state adducts preferably uses with the suspended state that is scattered in a kind of hydrocarbon solvent, and normally, its concentration (solid-state adducts)/(hydrocarbon solvent) is 1-1000g/L, is preferably 100-500g/L.Through this described solid titanium catalyst composition that makes corresponding to the described solid titanium catalyst composition [S3] that makes by above-mentioned contact method (P-3).
As for described hydrocarbon solvent, the solvent that is used to prepare described solid titanium catalyst composition [S1] all can use.Especially, aliphatic hydrocrbon such as octane and decane and aromatic hydrocarbon such as toluene and dimethylbenzene are preferred.
When the described solid titanium catalyst precursor of preparation [S2 '], the temperature that described solid-state adducts, described titanium compound contact with described compound with two or more ehter bonds as described electron donor(ED) (b2) is generally-70 ℃ to 200 ℃, and preferred temperature is-25 ℃ to 150 ℃.Contain titanium, magnesium, halogen and described compound through this described solid titanium catalyst composition precursor that makes [S2 '] with two or more ehter bonds.
Described have a temperature that the compound of two or more ehter bonds and the described solid titanium catalyst composition precursor that makes in a manner described [S2 '] further react, and normally between-70 ℃ to 200 ℃, preferred temperature is-25 ℃ to 150 ℃.Described consumption with compound of two or more ehter bonds is 0.01-5mol, is preferably 0.1-1mol, contains titanium, magnesium, halogen and described compound with two or more ehter bonds through this described solid titanium catalyst composition [S2] that makes.
In described solid titanium catalyst composition [S2], the ratio (atomic ratio) of halogen/titanium is 2-100, is preferably 4-90, described ratio (mol ratio) with compound/titanium of two or more ehter bonds is 0.01-100, be preferably 0.2-10, the ratio (atomic ratio) of magnesium/titanium is 2-100, is preferably 4-50.
The described solid titanium catalyst composition [S1] that is made by aforesaid method and the particle diameter of [S2] are 30-150 μ m, are preferably 30-100 μ m, more preferably 30-80 μ m.Particle diameter in this scope is preferred, and for instance, this is because cause that the mobility of particle of operating barrier can improve owing to described particle adhesion to polymerizer when preparing segmented copolymer.
Olefin polymerization catalyst of the present invention comprises through this described solid titanium catalyst composition [S] that obtains and a kind ofly contains a kind of Organometal compound catalyst composition [M] that is selected from the metal of I-III family in the periodic table of elements.Hereinafter, will be described in more detail described organometallic compound composition [M].
[Organometal compound catalyst composition [M]]
Used Organometal compound catalyst composition [M] for instance, comprises the organometallic compound of organometallic compound, alkylation I family's metal/aluminum complex and II family metal.
Described organo-aluminium compound for instance, comprises by R
a nAlX
3-nThe organo-aluminium compound of expression, wherein, R
aBe C
1-12Alkyl, X are halogen or hydrogen, and n is 1-3.
In above-mentioned general formula, for instance, R
aBe a kind of alkyl, cycloalkyl or aryl, the example comprises methyl, ethyl, n-propyl, sec.-propyl, isobutyl-, amyl group, hexyl, octyl group, cyclopentyl, cyclohexyl, phenyl and tolyl.
Described organo-aluminium compound comprises following compound: trialkylaluminium such as trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand and triisobutyl aluminium; Thiazolinyl aluminium such as prenyl aluminium; Dialkyl aluminum halide such as dimethylaluminum chloride and diethyl aluminum chloride; Aluminum alkyls sesquihalide such as methylaluminum sesquichloride and ethyl sesquialter aluminum chloride; Alkyllithium dihalide such as methylaluminum dichloride, ethylaluminum dichloride and sec.-propyl al dichloride; With alkyl aluminum hydride such as diethyl aluminium hydride and diisobutylaluminium hydride.
Used organo-aluminium compound comprises by R
a nAlY
3-nThe compound of expression, wherein, R
aDefine as above, Y is-OR
bGroup ,-OSiR
c 3Group ,-OAlR
d 2,-NR
e 2Group ,-SiR
f 3Group or-N (R
g) AlR
h 2, n is 1-2, R
b, R
c, R
d, and R
hBe methyl, ethyl, sec.-propyl, isobutyl-, cyclohexyl, phenyl etc. independently, R
eFor hydrogen,, methyl, ethyl, sec.-propyl, phenyl, trimethylsilyl etc., R
fAnd R
gBe methyl, ethyl etc. independently.
The particular instance of this class organo-aluminium compound comprises:
[i]R
a nAl(OR
b)
3-n
Dimethyl methoxy base aluminium, diethylaluminum ethoxide, diisobutyl aluminum methoxide etc.;
[ii]R
a nAl(OSiR
c 3)
3-n
Et
2Al(OSiMe
3)
(iso-Bu)
2Al(OSiMe
3)
(iso-Bu)
2Al (OSiEt
3) etc.;
[iii]R
a nAl(OAlR
d 2)
3-n
Et
2At
2lOAlEt
2
(iso-Bu)
2AlOAl (iso-Bu)
2Deng;
[iv]R
a nAl(NR
e 2)
3-n
Me
2AlNEt
2
Et
2AlNHMe
Me
2AlNHEt
Et
2AlN(Me
3Si)
2
(iso-Bu)
2AlN (Me
3Si)
2Deng;
[v]R
a nAl(SiR
f 3)
3-n
(iso-Bu)
2AlSiMe
3Deng;
[vi]R
a nAl(N(R
g)AlR
h 2)
3-n
Et
2AlN(Me)AlEt
2
(iso-Bu)
2AlN (Et) Al (iso-Bu)
2Deng.
In above-mentioned general formula, term Et represents ethyl, and iso-Bu represents isobutyl-, and Me represents methyl.
The preferred embodiment of this class organo-aluminium compound comprises by R
a 3Al, R
a nAl (OR
b)
3-nAnd R
a nAl (OAlR
d 2)
3-nThe organo-aluminium compound of expression.
Described alkylation I family metal/aluminum complex for instance, comprises by formula M
1AlR
j 4The compound of expression, wherein, M
1Be Li, Na or K, R
jBe C
1-15Alkyl, that specifically mentions has a LiAl (C
2H
5)
4, LiAl (C
7H
15)
4Deng.
The organometallic compound of described II family metal comprises by general formula R
kR
1M
2The expression compound, wherein, R
kAnd R
1Represent C independently
1-15Alkyl or halogen, they can be identical, also can be different, condition is that these two groups are not halogen simultaneously, and M
2Be Mg, Zn or Cd.Especially, described organometallic compound comprise zinc ethyl, magnesium ethide,, butyl ethyl magnesium, ethylmagnesium chloride and butylmagnesium chloride.
These compounds can use in their mixture.
The consumption of described Organometal compound catalyst composition [M] will explain in for " process for olefin polymerization " at described title subsequently.
[electron donor(ED) (c)]
In the present invention, above-mentioned electron donor(ED) (b) and/or electron donor(ED) (c) if necessary, can use with described Organometal compound catalyst composition [M].Described electron donor(ED) (c) is preferably a kind of silicoorganic compound.This silicoorganic compound for instance, comprise the compound of being represented by following general formula:
R
nSi(OR’)
4-n
Wherein, R and R ' represent alkyl independently, and n satisfies the relational expression of 0＜n＜4.
As for the silicoorganic compound of representing by above-mentioned general formula, can exemplify following compound: the trimethylammonium methoxy silane, trimethylethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diisopropyl dimethoxy silane, tertiary butyl methyl dimethoxysilane, tertiary butyl methyldiethoxysilane, the tert-pentyl methyldiethoxysilane, phenyl methyl dimethoxy silane, dicyclohexyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, the cyclohexyl methyl diethoxy silane, methyltrimethoxy silane, ethyl triethoxysilane, vinyltrimethoxy silane, methyltrimethoxy silane, the n-propyl triethoxyl silane, Union carbide A-162, ethyl triethoxysilane, vinyltriethoxysilane, tertiary butyl triethoxyl silane, phenyl triethoxysilane, the chloro triethoxyl silane, vinyl three butoxy silanes, cyclohexyl trimethoxy silane, the cyclohexyl triethoxyl silane, trimethyl phenoxysilane, vinyltriacetoxy silane, dimethyl tetraethoxy sily oxide, the cyclopentyl Trimethoxy silane, 2-methylcyclopentyl Trimethoxy silane, the cyclopentyl triethoxyl silane, dicyclopentyl dimethoxyl silane, two cyclopentyl diethoxy silanes, three cyclopentyl methoxy silane, three cyclopentyl Ethoxysilanes, two cyclopentyl-methyl methoxy silane, two cyclopentyl ethyl methoxy silane, the hexenyl Trimethoxy silane, two cyclopentyl-methyl Ethoxysilanes, cyclopentyl dimethyl methyl TMOS, cyclopentyl diethyl methoxy silane, with the cyclopentyl dimethylethoxysilane.
In these materials, that preferably uses is ethyl triethoxysilane, n-propyl triethoxyl silane, tertiary butyl triethoxyl silane, vinyltriethoxysilane, vinyl three butoxy silanes, hexichol dimethoxy silane, phenyl methyl dimethoxy silane, dicyclohexyl dimethoxy silane, cyclohexyl methyl dimethoxy silane, phenyl triethoxysilane, dicyclopentyl dimethoxyl silane, hexenyl Trimethoxy silane, cyclopentyl triethoxyl silane, three cyclopentyl methoxy silane and cyclopentyl dimethyl methyl TMOS.
These silicoorganic compound can use in their mixture.
When above-mentioned electron donor(ED) (b) with (c) if desired with described Organometal compound catalyst composition [M] when using, the quantity of used electron donor(ED) will be described in for " process for olefin polymerization " at following title.
[process for olefin polymerization]
In process for olefin polymerization of the present invention, olefinic polyreaction is that the application of the invention olefin polymerization catalyst carries out.
In process for olefin polymerization of the present invention, described polyreaction also can be carried out in the presence of a kind of pre-polymerized catalyst that makes by the prepolymerization at alpha-olefin in the presence of the olefin polymerization catalyst of the present invention.This prepolymerization reaction is by with respect to the described olefin polymerization catalyst of every gram, and quantity is 0.1-1000g, is preferably 0.3-500g, and the prepolymerization that is preferably the alpha-olefin of 1-200g is especially carried out.
In described prepolymerization reaction, described catalyzer can use with the concentration that catalyst concn is higher in the system of post-polymerization.
In described prepolymerization reaction, the concentration of described solid titanium catalyst composition [S] is represented with the titanium atom of every L liquid medium, normally within the scope of about 0.001-200mmol, is preferably about 0.01-50mmol, is preferably 0.1-20mmol especially.
Described Organometal compound catalyst composition [M] in the prepolymerization reaction, preferably use with such quantity, with respect to the described solid titanium catalyst composition of every gram [S], enable to form the polymkeric substance that quantity is 0.1-1000g, be preferably the 0.3-500g polymkeric substance, the consumption of described catalyst component [M], with respect to every mole of titanium atom in the described solid titanium catalyst composition [S], be generally about 0.1-300mol, be preferably about 0.5-100mol, be preferably 1-50mol especially.
In described prepolymerization reaction, described electron donor(ED) (b) or electron donor(ED) (c) are as a kind of silicoorganic compound, also can use if necessary, and the consumption of these compositions, with respect to every mole of titanium atom in the described solid titanium catalyst composition [S], be 0.1-50mol, be preferably 0.5-30mol, more preferably 1-10mol.
After alkene and described catalyst component added in a kind of unreactive hydrocarbons medium, described prepolymerization reaction can be carried out under mild conditions.
Used unreactive hydrocarbons medium for instance, comprises aliphatic hydrocrbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; Alicyclic hydrocarbon such as pentamethylene, hexanaphthene and methylcyclopentane; Aromatic hydrocarbon such as benzene, toluene and dimethylbenzene; With halohydrocarbon such as vinylchlorid and chlorobenzene; Or its mixture.
In these unreactive hydrocarbons media, aliphatic hydrocrbon is particularly preferred.When using described unreactive hydrocarbons medium, described prepolymerization reaction is preferably carried out in batch systems.
A kind of replacement scheme is, described prepolymerization reaction is carried out as solvent or not containing under the solvent condition substantially by using described alkene self.In this case, described prepolymerization reaction is preferably carried out continuously.
The alkene that is used for described prepolymerization reaction is preferably propylene, it with described polyreaction subsequently in used alkene can be identical, also can be different.
The temperature of reaction of prepolymerization reaction normally between about-20 ℃ to 100 ℃ scopes, is preferably between-20 ℃ to 80 ℃ more preferably 0-40 ℃.
In described prepolymerization reaction, also can use molecular weight regulator such as hydrogen.
As mentioned above, described prepolymerization reaction is performed such with wishing, makes formed polymkeric substance, and with respect to the described solid titanium catalyst composition of every gram [S], its quantity is about 0.1-1000g, is preferably about 0.3-500g, more preferably 1-200g.When the excessive number of the described polymkeric substance that forms in described prepolymerization reaction, the efficient of producing described olefin polymer just may reduce.
Described prepolymerization reaction can intermittently or in the continuous system carried out.
Now, to polyreaction of after described prepolymerization reaction, carrying out or the polyreaction of not carrying out described prepolymerization reaction, describe.
Can be used for the alkene in the described polyreaction, comprise ethene and C
3-20Alpha-olefin such as propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-laurylene, 1-tetradecylene, 1-hexadecylene, 1-octadecylene and 1-icosa alkene, wherein, propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferred the uses.
In polymerisation process of the present invention, above-mentioned these alkene of mentioning can use separately, perhaps, use with its mixture.Can comprise aromatic vinyl compound such as vinylbenzene and phenylallene with the initial substance that ethene and alpha-olefin use; Alicyclic ethylene based compound such as vinyl cyclohexane; Cycloolefin such as cyclopentenes, suberene, norbornylene, tetracyclododecen and have the compound of a plurality of unsaturated link(age)s, for example conjugation or unconjugated diene such as isoprene and divinyl.
In the present invention, described prepolymerization reaction and polyreaction both can liquid-phase polymerization such as solution polymerization and suspension polymerization carry out, also can carry out by gas phase polymerization.
When described polyreaction is a reaction formation with slurry polymerization when carrying out, described reaction solvent can be the described unreactive hydrocarbons that are used for the prepolymerization reaction, perhaps is a kind of alkene that is in a liquid state when described temperature of reaction.
In polymerisation process of the present invention, the common consumption of described solid titanium catalyst composition [S] is about 0.0001-0.5mmol, is preferably about 0.005-0.1mmol.And, described Organometal compound catalyst composition [M], with respect to every mole of titanium atom in the pre-polymerized catalyst composition described in the described polymerization reaction system, its common consumption is about 1-2000mol, is preferably about 5-500mol.Described electron donor(ED) (c), with respect to every mole of described Organometal compound catalyst composition [M], its consumption is 0.001-50mol, is preferably 0.01-30mol, more preferably 0.05-20mol.
The molecular weight of resulting polymkeric substance can be adjusted by use hydrogen in described polyreaction, to obtain a kind of polymkeric substance with very big melt flow rate (MFR).
In polyreaction of the present invention, the temperature that is used for olefinic polyreaction is generally about 20-100 ℃, is preferably about 50-90 ℃, and reaction pressure is set in normal atmosphere usually to 100kg/cm
2Between, be preferably about 2-50kg/cm
2In polyreaction of the present invention, described polyreaction can be carried out in batch systems, semicontinuous or continuous system.And, described polyreaction also can be under the differential responses condition in two steps or multistep carry out.
The olefin polymer that obtains like this can be homopolymer, unregulated polymer or segmented copolymer.
The alkene that uses above-mentioned olefin polymerization catalyst is the polyreaction of propylene particularly, can obtain a kind of isotactic index (I.I.) is 70% or bigger, be preferably 85% or bigger, be preferably 95% or bigger propene polymer especially, represent with the resistates that adopts the extraction of boiling heptane.
Described polymkeric substance compares to the polymkeric substance that is made by ordinary method, and the Mw/Mn with lower expression molecular weight distribution is than (it is recorded by gel permeation chromatography (GPC)), generally can obtain to have Mw/Mn in the present invention than being 5 or littler polymkeric substance.
In the present invention, except mentioned component, described olefin polymerization catalyst also can contain the composition that other is of value to olefinic polyreaction.
Embodiment
Hereinafter, will the present invention will be described in more detail by means of embodiment, still, the present invention is not limited to these embodiment.
In the following embodiments, the particle diameter of the tap density of described propene polymer and melt flow rate (MFR), described solid titanium catalyst composition measures as follows:
(1) tap density: record according to JIS K-6721.
(2) melt flow rate (MFR) (MFR): record according to ASTM D1238E (190 ℃).
(3) method of measurement described solid titanium catalyst composition [S] particle diameter: by using one
Plant by Horiba, the centrifugal settling method of the CAPA-300 grain analyser that Ltd makes is analyzed.
Embodiment 1
(preparation solid titanium catalyst composition [S1])
One has the high-speed stirring apparatus that internal volume is 2L (Tokushukika kogyo Co. Ltd.), adopts nitrogen fully to purge, and afterwards, the 700ml purifying kerosene of packing into, 10g commerce can get magnesium chloride, 24.2g ethanol and 3g Emasol 320
TM(the anhydrosorbitol SUNSOFT Q-182S is made by Kao Atlas) improves described system temperature under stirring action, described mixture stirred 30 minutes with the 800rpm rotating speed at 120 ℃.Teflon (registered trademark) pipeline that described reaction mixture under high-speed stirring is 5mm via an internal diameter, be sent to one its contain previous in-10 ℃ of 2L vials (having agitator) that carry out refrigerative 1L purifying kerosene.After employing purifying normal hexane carries out thorough washing by filtration to described purifying solid, just can obtain a kind of solid-state adducts, it has the magnesium chloride that 1mol is cooperated by 2.8mol ethanol.
Be suspended in the whole solid-state adducts in the 30ml decane, count 46.2mmol, under stirring action, be incorporated in the titanium tetrachloride of the 200ml that remains on-20 ℃ with magnesium atom.This mixture is heated to 80 ℃ with time of 5 hours, when described temperature reaches 80 ℃, to wherein adding 1.9g o-benzene butyl phthalate ester (DIBP), heats this mixture to 120 ℃ with 40 minutes time.Under stirring action, this mixture kept 90 minutes at 120 ℃.
After continuing reaction end in 90 minutes, collect solid by heat filtering, and be suspended in the 200ml titanium tetrachloride once more described solid and heating, when described temperature reached 130 ℃, described mixture kept 45 minutes under stirring action.
After reaction finishes, collect solid by heat filtering once more, and it is carried out thorough washing, up in washing soln, no longer detecting the free titanium compound in 100 ℃ of employing decane and hexane.The described solid titanium catalyst composition that in this way makes is stored with the decane slurry form, and its sample is carried out drying, forms to detect described catalyzer.
Contain through this described solid titanium catalyst composition [S1] that makes composition: 2.4wt% titanium, 20wt% magnesium, 7.4wt%DIBP and 0.5wt% ethanol resistates.The particle diameter of described catalyzer is 40 μ m.
(preparation pre-polymerized catalyst)
With 100ml purifying normal hexane, 3mmol triethyl aluminum with count the solid titanium catalyst composition that in embodiment 1, makes of 1.0mmol with titanium atom, be incorporated in the 200mL four neck glass reactors that dispose agitator, afterwards, under 20 ℃, the speed of propylene with 3.2NL/h is fed in the described mixture, continues 1 hour.
After propylene feed is finished, adopt nitrogen that described reactor is purged, and carry out twice washing (comprise and remove supernatant liquid and introduce the purifying normal hexane), the pre-polymerized catalyst composition that obtains is suspended in the purifying normal hexane once more, and whole suspension is transferred in the catalyzer bottle.
(polyreaction)
It is in the polymerization reactor of 2L that 500g propylene and 1NL hydrogen at room temperature are incorporated into an internal volume, then heat, in the time of 60 ℃, to wherein add 0.5mmol triethyl aluminum, 0.1mmol cyclohexyl methyl dimethoxy silane (=CMMS), count the described pre-polymerized catalyst composition of 0.004mmol with titanium atom, described polymerization reactor remains on 70 ℃.After described polyreaction continues to carry out 1 hour, described propylene is purged.
Output is 237g, and the apparent bulk density of described polymkeric substance is 0.48g/ml, and MFR is 3.9dg/min, and I.I. is 98.4%, and activity is 59.3kg-PP/mmol-Ti.
Embodiment 2
Repeat the step identical with embodiment 1, then difference at the 2-isobutyl--2-sec.-propyl-1 that adopts 2.3g, the alternative DIBP of 3-Propanal dimethyl acetal is as described electron donor(ED) (b).Composition through this described solid titanium catalyst composition that makes contains: 2-isobutyl--2-sec.-propyl-1 of 3.1wt% titanium, 18wt% magnesium, 14.1wt%, 3-Propanal dimethyl acetal and 0.9wt% ethanol resistates.The particle diameter of described catalyzer is 36 μ m.
Carry out the polyreaction identical with embodiment 1, difference is to be to use above-mentioned catalyzer.Output is 365g, and the apparent bulk density of described polymkeric substance is 0.44g/ml, and MFR is 12.0dg/min, and I.I. is 97.2%, and activity is 91.1kg-PP/mmol-Ti.
Embodiment 3
Repeat the step identical with embodiment 1, then difference at the 2-isobutyl--2-isopentyl-1 that adopts 2.5g, the alternative DIBP of 3-Propanal dimethyl acetal is as described electron donor(ED) (b).Composition through this described solid titanium catalyst composition that makes contains: 2-sec.-propyl-2-isopentyl-1 of 3.0wt% titanium, 17wt% magnesium, 13.1wt%, 3-Propanal dimethyl acetal and 0.8wt% ethanol resistates.The particle diameter of described catalyzer is 39 μ m.
Carry out the polyreaction identical with embodiment 1, difference is to be to use above-mentioned catalyzer.Output is 255g, and the apparent bulk density of described polymkeric substance is 0.43g/ml, and MFR is 11.0dg/min, and I.I. is 97.2%, and activity is 128.0kg-PP/mmol-Ti.
Embodiment 4
Repeat the step identical with embodiment 1, it is to adopt the alternative 30ml decane of 30ml toluene when the described solid titanium catalyst composition of preparation that difference is.Composition through this described solid titanium catalyst composition that makes contains: the DIBP of 2.4wt% titanium, 20wt% magnesium, 6.3wt% and 0.3wt% ethanol resistates.The particle diameter of described catalyzer is 42 μ m.
Carry out the polyreaction identical with embodiment 1, difference is to be to use above-mentioned catalyzer.Output is 313g, and the apparent bulk density of described polymkeric substance is 0.45g/ml, and MFR is 2.5dg/min, and I.I. is 98.4%, and activity is 78.3kg-PP/mmol-Ti.
Embodiment 5
Repeat the step identical with embodiment 2, it is to adopt the alternative 30ml decane of 30ml toluene when the described solid titanium catalyst composition of preparation that difference is.Composition through this described solid titanium catalyst composition that makes contains: 2-isobutyl--2-sec.-propyl-1 of 3.2wt% titanium, 18wt% magnesium, 13.4wt%, 3-Propanal dimethyl acetal and 0.8wt% ethanol resistates.The particle diameter of described catalyzer is 38 μ m.
Carry out the polyreaction identical with embodiment 1, difference is to be to use above-mentioned catalyzer.Output is 157g, and the apparent bulk density of described polymkeric substance is 0.44g/ml, and MFR is 5.4dg/min, and I.I. is 98.0%, and activity is 78.5kg-PP/mmol-Ti.
Embodiment 6
Repeat the step identical with embodiment 1, difference is when the described pre-polymerized catalyst that makes among the embodiment 1 is used for described polyreaction, does not use the cyclohexyl methyl dimethoxy silane as electron donor(ED) (c).Output is 228g, and the apparent bulk density of described polymkeric substance is 0.44g/ml, and MFR is 14.0dg/min, and I.I. is 95.0%, and activity is 114.0kg-PP/mmol-Ti.
Comparative Examples 1
The whole solid-state adducts that will make in embodiment 1 is counted 46.2mmol with magnesium atom, under stirring action, with solid-state form, is incorporated in the titanium tetrachloride of the 200ml that remains on-20 ℃.This mixing solutions is heated to 80 ℃ with 5 hours time, when described temperature reaches 80 ℃, to wherein adding 1.9g o-benzene butyl phthalate ester (DIBP), heats this mixture to 120 ℃ with 40 minutes time.Under stirring action, this mixture kept 90 minutes at 120 ℃.
After continuing reaction end in 90 minutes, collect solid by heat filtering, and be suspended in the 200ml titanium tetrachloride once more described solid and heating, when described temperature reached 130 ℃, described mixture kept 45 minutes under this temperature under stirring action.
After reaction finishes, collect solid by heat filtering once more, and it is washed, up in washing soln, no longer detecting the free titanium compound in 100 ℃ of employing decane and hexane.The described solid titanium catalyst composition that in this way makes is stored with the decane slurry form, and its sample is carried out drying, forms to detect described catalyzer.Become to be grouped into through this described solid titanium catalyst that makes and contain: 3.2wt% titanium, 17wt% magnesium, 13.8wt%DIBP and 0.5wt% ethanol resistates.The particle diameter of described catalyzer is 40 μ m.
Carry out the polyreaction identical with embodiment 1, difference is to be to use above-mentioned catalyzer.Output is 163g, and the apparent bulk density of described polymkeric substance is 0.48g/ml, and MFR is 4.5dg/min, and I.I. is 98.2%, and activity is 40.9kg-PP/mmol-Ti.
Comparative Examples 2
Repeat the step identical with Comparative Examples 1, then difference at the 2-isobutyl--2-sec.-propyl-1 that adopts 2.3g, the alternative DIBP of 3-Propanal dimethyl acetal is as described electron donor(ED) (b).Composition through this described solid titanium catalyst composition that makes contains: 2-isobutyl--2-sec.-propyl-1 of 4.1wt% titanium, 15wt% magnesium, 18.2wt%, 3-Propanal dimethyl acetal and 0.9wt% ethanol resistates.The particle diameter of described catalyzer is 38 μ m.
Carry out the polyreaction identical with Comparative Examples 1, difference is to be to use above-mentioned catalyzer.Output is 253g, and the apparent bulk density of described polymkeric substance is 0.43g/ml, and MFR is 12.0dg/min, and I.I. is 97.1%, and activity is 63.3kg-PP/mmol-Ti.
The above results all concentrates among the following table 1.
Table 1
1) o-benzene butyl phthalate ester
2) 2-isobutyl--2-sec.-propyl-1, the 3-Propanal dimethyl acetal
3) 2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal
4) cyclohexyl methyl dimethoxy silane
Embodiment 7
(preparation solid titanium catalyst composition [S3])
One has the high-speed stirring apparatus that internal volume is 2L (Tokushukika kogyo Co. Ltd.), adopts nitrogen fully to purge, and afterwards, the 700ml purifying kerosene of packing into, 10g commerce can get magnesium chloride, 24.2g ethanol and 3g Emasol 320
TM(the anhydrosorbitol SUNSOFT Q-182S is made by Kao Atlas) improves described system temperature under stirring action, described mixture stirred 30 minutes with the 800rpm rotating speed at 120 ℃.Described reaction mixture under high-speed stirring, via Teflon (registered trademark) pipeline that an internal diameter is 5mm, be sent to one its contain previous in-10 ℃ of 2L vials (having agitator) that carry out refrigerative 1L purifying kerosene.After employing purifying normal hexane carries out thorough washing by filtration to the solid that produces, just can obtain a kind of solid-state adducts, it has the magnesium chloride that 1mol is cooperated by 2.8mol ethanol.
Be suspended in the whole solid-state adducts in the 30ml decane, count 46.2mmol, under stirring action, be incorporated in the titanium tetrachloride of the 200ml that remains on-20 ℃ with magnesium atom.This mixture is heated to 80 ℃ with 5 hours time, and when described temperature reached 80 ℃, to the 2-isobutyl--2-sec.-propyl-1 that wherein adds 1.4g, the 3-Propanal dimethyl acetal heated this mixture to 120 ℃ with 40 minutes time.Under stirring action, this mixture kept 90 minutes at 120 ℃.
After continuing reaction end in 90 minutes, collect solid by heat filtering, and be suspended in the 200ml titanium tetrachloride once more described solid and heating, when described temperature reaches 130 ℃, to the 2-isobutyl--2-sec.-propyl-1 that wherein adds 0.9g, 3-Propanal dimethyl acetal, described mixture kept 45 minutes in 130 ℃ under stirring action.
After continuing reaction end in 45 minutes, collect solid by heat filtering, and be suspended in the 200ml titanium tetrachloride once more described solid and heating, when described temperature reached 130 ℃, described mixture kept 45 minutes under this temperature under stirring action.After this reaction finishes, collect solid by heat filtering once more, and it is carried out thorough washing, up in washing soln, no longer detecting the free titanium compound in 100 ℃ of employing decane and hexane.The described solid titanium catalyst composition that in this way makes is stored with the decane slurry form, and its sample is carried out drying, forms to detect described catalyzer.
Contain through this described solid titanium catalyst composition [S3] that makes composition: 2-isobutyl--2-sec.-propyl-1 of 2.7wt% titanium, 19wt% magnesium, 14.2wt%, 3-Propanal dimethyl acetal and 0.2wt% ethanol resistates.The particle diameter of described catalyzer is 38 μ m.
(polyreaction)
It is in the polymerization reactor of 2L that 500g propylene and 1NL hydrogen at room temperature are incorporated into an internal volume, then, to wherein adding 0.5mmol triethyl aluminum, 0.1mmol cyclohexyl methyl dimethoxy silane, count the described solid titanium catalyst composition [S3] of 0.004mmol, and described polymerization reactor is heated to 70 ℃ apace with titanium atom.After carrying out 1 hour under 70 ℃, stop described reaction in described polyreaction, and described propylene is purged by small amount of methanol.
Output is 446g, and the apparent bulk density of described polymkeric substance is 0.43g/ml, and MFR is 10.5dg/min, and I.I. is 97.3%, and activity is 112.0kg-PP/mmol-Ti.
Embodiment 8
(preparation solid titanium catalyst composition [S3])
By preparing catalyzer, so difference is adopting the described solid-state adducts of counting 54.1mmol with magnesium atom with embodiment 7 same procedure.
(polyreaction)
By carrying out the polyreaction of propylene with embodiment 7 same procedure, difference is the catalyzer that uses present embodiment to make.Output is 508g, and the apparent bulk density of described polymkeric substance is 0.43g/ml, and MFR is 11.0dg/min, and I.I. is 97.3%, and activity is 127.0kg-PP/mmol-Ti.
Embodiment 9
(preparation solid titanium catalyst composition [S2])
By preparing the solid titanium catalyst composition with embodiment 7 same procedure, difference is not used decane at solid titanium catalyst composition described in the preparation embodiment 7 time.
(polyreaction)
By carrying out the polyreaction of propylene with embodiment 7 same procedure, difference is the catalyzer that uses present embodiment to make.Output is 154g, and the apparent bulk density of described polymkeric substance is 0.42g/ml, and MFR is 10.0dg/min, and I.I. is 97.3%, and activity is 77.2kg-PP/mmol-Ti.
Comparative Examples 3
Be suspended in the whole solid-state adducts that makes among the embodiment 7 in the 30ml decane, count 46.2mmol, under stirring action, be incorporated in the titanium tetrachloride of the 200ml that remains on-20 ℃ with magnesium atom.This mixture is heated to 80 ℃ with 5 hours time, and when described temperature reached 80 ℃, to the 2-isobutyl--2-sec.-propyl-1 that wherein adds 2.3g, the 3-Propanal dimethyl acetal heated this mixture to 120 ℃ with 40 minutes time.Under stirring action, this mixture kept 90 minutes at 120 ℃.
After continuing reaction end in 90 minutes, collect solid by heat filtering, and be suspended in the 200ml titanium tetrachloride once more described solid and heating, when described temperature reached 130 ℃, described mixture kept 45 minutes under this temperature under stirring action.After this reaction finishes, collect solid by heat filtering once more, and it is carried out thorough washing, up in washing soln, no longer detecting the free titanium compound in 100 ℃ of employing decane and hexane.
The described solid titanium catalyst composition that in this way makes is stored with the decane slurry form, and its sample is carried out drying, forms to detect described catalyzer.
Become to be grouped into through this described solid titanium catalyst that makes and contain: 2-isobutyl--2-sec.-propyl-1 of 2.7wt% titanium, 18wt% magnesium, 15.6wt%, 3-Propanal dimethyl acetal and 0.7wt% ethanol resistates.The particle diameter of described catalyzer is 38 μ m.
(polyreaction)
By carrying out propylene polymerization with embodiment 7 same procedure, difference is the catalyzer that uses this Comparative Examples to make.Output is 341g, and the apparent bulk density of described polymkeric substance is 0.4g/ml, and MFR is 11.5dg/min, and I.I. is 97.2%, and activity is 85.1kg-PP/mmol-Ti.
Embodiment 10
(preparation pre-polymerized catalyst)
With 100ml purifying normal hexane, 3mmol triethyl aluminum with count the described solid titanium catalyst composition [S2] that in embodiment 7, makes of 1.0mmol with titanium atom, in nitrogen atmosphere, be incorporated in the 200mL four neck glass reactors that dispose agitator, afterwards, under 20 ℃, the speed of propylene with 3.2NL/h is fed in the described mixture, continues l hour.
After propylene feed is finished, adopt nitrogen that described reactor is purged, and carry out twice washing (comprise and remove supernatant liquid and introduce the purifying normal hexane), the prepolymerization catalysts composition that obtains is suspended in the purifying normal hexane once more, and whole suspension is transferred in the catalyzer bottle.
(polyreaction)
It is in the polymerization reactor of 2L that 500g propylene and 1NL hydrogen at room temperature are incorporated into an internal volume, then be heated to 60 ℃, to wherein adding 0.5mmol triethyl aluminum, 0.1mmol cyclohexyl methyl dimethoxy silane, count the described prepolymerization catalysts composition of 0.004mmol with titanium atom, and described polymerization reactor is heated to 70 ℃ apace.After carrying out 1 hour under 70 ℃, stop described reaction in described polyreaction, and described propylene is purged by small amount of methanol.Output is 298g, and the apparent bulk density of described polymkeric substance is 0.46g/ml, and MFR is 11.0dg/min, and I.I. is 97.4%, and activity is 74.6kg-PP/mmol-Ti.
The above results all concentrates among the following table 2.
Table 2
1) polymerization system of the described pre-polymerized catalyst of use.
As mentioned above, solid titanium catalyst composition of the present invention [S] can be used to obtain that a kind of to have more a highly active catalytic active and produce a kind of olefin polymerization catalyst with high stereospecific polymkeric substance, and does not need to use electron donor(ED) when polyreaction.By in polyreaction, using described electron donor(ED) (c) simultaneously, can make and a kind ofly have more high catalytic activity and produce a kind of olefin polymerization catalyst with high stereospecific polymkeric substance.
Olefin polymerization catalyst of the present invention comprises described solid titanium catalyst composition [S] and a kind ofly contains a kind of Organometal compound catalyst composition [M] that is selected from the metal of I-III family in the periodic table of elements that process for olefin polymerization of the present invention comprises a kind of monomeric polyreaction or copolyreaction that is selected from alpha-olefin of using described olefin polymerization catalyst.Therefore, according to olefin polymerization catalyst of the present invention and described process for olefin polymerization, polyreaction can very high catalytic activity be carried out efficiently, makes a kind of polymkeric substance with high stereospecific.
Claims (6)
1. solid titanium catalyst composition that is used for olefinic polyreaction, it contains titanium, magnesium, halogen and a kind of electron donor(ED) (b), it is by under a kind of unreactive hydrocarbons solvent coexistence, a kind of solid adduct of being made up of a kind of magnesium compound and a kind of electron donor(ED) (a) is contacted with suspended state with a kind of liquid titanium compound with a kind of electron donor(ED) (b) make.
2. solid titanium catalyst composition that is used for olefinic polyreaction, it contains titanium, magnesium, halogen and a kind ofly has two or more compounds via the ehter bond of a plurality of atoms (b1), it is to make by a kind of solid adduct of being made up of a kind of magnesium compound and a kind of electron donor(ED) (a) is contacted with a kind of liquid titanium compound with a kind of electron donor(ED) (b1) in batches repeatedly, wherein with respect to every mole of magnesium in the described solid-state adducts, total consumption of described compound (b1) is 0.1-2.0mol.
3. the solid titanium catalyst composition that is used for olefinic polyreaction as claimed in claim 1 is characterized in that described electron donor(ED) (b) is a kind of compound with two or more ehter bonds.
4. as any one described solid titanium catalyst composition that is used for olefinic polyreaction in the claim 1 to 3, it is characterized in that particle diameter is 30-150 μ m.
5. catalyzer that is used for olefinic polyreaction comprises among the claim 1-4 each described solid titanium catalyst composition that is used for olefinic polyreaction and a kind ofly contains a kind of Organometal compound catalyst composition that is selected from the metal of periodic table of elements I-III family.
6. method that is used for olefinic polyreaction, it comprises by using the described catalyzer that is used for olefinic polyreaction of claim 5, at least a ethene and the C of being selected from
3-20The alkene of alpha-olefin carries out polymerization.
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| JP2002102694 | 2002-04-04 | ||
| JP102694/2002 | 2002-04-04 | ||
| JP102701/2002 | 2002-04-04 | ||
| JP2002102701 | 2002-04-04 |
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| US (1) | US7220696B2 (en) |
| EP (1) | EP1490413A4 (en) |
| KR (1) | KR100615936B1 (en) |
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| US7888438B2 (en) * | 2005-01-19 | 2011-02-15 | Mitsui Chemicals, Inc. | Catalyst for olefin polymerization and process for olefin polymerization |
| ES2536729T3 (en) * | 2005-01-19 | 2015-05-28 | Mitsui Chemicals, Inc. | Production process of an olefinic polymer |
| EP1857475A1 (en) * | 2006-04-24 | 2007-11-21 | Total Petrochemicals Research Feluy | Use of Ziegler-Natta catalyst to make a polypropylene homopolymer or random copolymer having a high melt flow rate |
| PL2013250T3 (en) * | 2006-04-24 | 2009-12-31 | Total Res & Technology Feluy | Process for the production of propylene polymers having a low ash content |
| PL2013249T3 (en) | 2006-04-24 | 2015-11-30 | Total Res & Technology Feluy | Use of a ziegler-natta catalyst to make a polypropylene random copolymer having a high melt flow rate |
| JP2010510361A (en) * | 2006-11-21 | 2010-04-02 | バーゼル・ポリオレフィン・イタリア・ソチエタ・ア・レスポンサビリタ・リミタータ | Catalyst component for polymerization of olefins |
| KR100866615B1 (en) * | 2007-01-18 | 2008-11-04 | 고려대학교 산학협력단 | Method and apparatus for transmitting and receiving a signal in a communication system |
| EP2206731B1 (en) * | 2007-11-01 | 2013-08-28 | Mitsui Chemicals, Inc. | Solid titanium catalyst component, olefin polymerization catalyst, and olefin polymerization method |
| US20100273641A1 (en) | 2007-12-21 | 2010-10-28 | Linfeng Chen | Self-Limiting Catalyst Composition with Non-Phthalate Internal Donor |
| JP5374498B2 (en) * | 2008-04-08 | 2013-12-25 | 三井化学株式会社 | Solid titanium catalyst component for ethylene polymerization, catalyst for ethylene polymerization, and method for polymerizing ethylene |
| CN102399328B (en) * | 2010-09-16 | 2013-07-03 | 中国石油化工股份有限公司 | Catalyst component for olefin polymerization and catalyst therefrom |
| CN103665230B (en) * | 2012-09-18 | 2016-02-10 | 中国石油天然气股份有限公司 | A kind of ethylene/alpha-olefin catalyst for copolymerization and Synthesis and applications thereof |
| JP5984173B2 (en) | 2012-09-24 | 2016-09-06 | インディアン オイル コーポレーション リミテッド | Process for preparing a catalyst for olefin polymerization |
| EP3647329A4 (en) | 2017-06-30 | 2021-03-24 | Mitsui Chemicals, Inc. | Propylene-based polymer, method for preparing same, propylene-based resin composition, and molded body |
| JP7283203B2 (en) | 2019-04-25 | 2023-05-30 | 住友化学株式会社 | Method for producing propylene polymer |
| JP2021161216A (en) | 2020-03-31 | 2021-10-11 | 住友化学株式会社 | Solid catalyst component for olefin polymerization |
| EP4155324A3 (en) | 2021-09-22 | 2023-05-03 | Sumitomo Chemical Company, Limited | Method for producing solid catalyst component for olefin polymerization, method for producing catalyst for olefin polymerization, and method for producing olefin polymer |
| JP2023103559A (en) | 2022-01-14 | 2023-07-27 | 住友化学株式会社 | Heterophasic propylene polymerization material and olefin polymer |
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| IT1245250B (en) * | 1991-03-27 | 1994-09-13 | Himont Inc | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINE |
| IT1274253B (en) * | 1995-02-21 | 1997-07-15 | Himont Inc | PROCESS FOR THE PREPARATION OF SOLID CATALYTIC COMPONENTS FOR THE POLYMERIZATION OF OLEFINE |
| GB2325004B (en) * | 1997-05-09 | 1999-09-01 | Samsung General Chemicals Co | A catalyst for polymerization and copolymerization of olefins |
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- 2003-04-03 KR KR1020047011794A patent/KR100615936B1/en active IP Right Grant
- 2003-04-03 EP EP03745902A patent/EP1490413A4/en not_active Withdrawn
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| JPH03294310A (en) * | 1990-04-13 | 1991-12-25 | Mitsui Petrochem Ind Ltd | Production of ethylene/alpha-olefin copolymer |
| US5780378A (en) * | 1992-08-31 | 1998-07-14 | Mitsui Petrochemical Industries, Ltd. | Solid titanium catalyst component for olefin polymerization, process for preparing the same, catalyst for olefin polymerization and process for olefin polymerization |
| JPH06279526A (en) * | 1993-03-24 | 1994-10-04 | Mitsui Petrochem Ind Ltd | Solid titanium catalyst component for polymerization of olefin, catalyst for polymerization of olefin, and polymerization of olefin by using the same catalyst |
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| US20040259721A1 (en) | 2004-12-23 |
| WO2003085006A1 (en) | 2003-10-16 |
| CN1642994A (en) | 2005-07-20 |
| EP1490413A4 (en) | 2008-05-14 |
| US7220696B2 (en) | 2007-05-22 |
| KR100615936B1 (en) | 2006-08-28 |
| EP1490413A1 (en) | 2004-12-29 |
| KR20040082403A (en) | 2004-09-24 |
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